Ultrafast XANES Monitors Femtosecond Sequential Structural Evolution in Photoexcited Coenzyme B12
Abstract
Polarized X-ray absorption near-edge structure (XANES) at the Co K-edge and broadband UV-vis transient absorption are used to monitor the sequential evolution of the excited-state structure of coenzyme B12 (adenosylcobalamin) over the first picosecond following excitation. The initial state is characterized by sub-100 fs sequential changes around the central cobalt. These are polarized first in the y-direction orthogonal to the transition dipole and 50 fs later in the x-direction along the transition dipole. Expansion of the axial bonds follows on a ca. 200 fs time scale as the molecule moves out of the Franck-Condon active region of the potential energy surface. On the same 200 fs time scale there are electronic changes that result in the loss of stimulated emission and the appearance of a strong absorption at 340 nm. These measurements provide a cobalt-centered movie of the excited molecule as it evolves to the local excited-state minimum.
- Authors:
-
[1];
[2];
[4];
[6];
[4];
[4];
[7]
- Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemistry
- Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Physics
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
- Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemistry and Dept. of Biophysics
- Univ. of Michigan, Ann Arbor, MI (United States). Applied Physics Program
- Univ. of Louisville, KY (United States). Dept. of Chemistry
- Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemistry, Dept. of Physics, and Dept. of Biophysics
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1605287
- Grant/Contract Number:
- AC02-76SF00515; 1464584; 1565795; 1836435
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
- Additional Journal Information:
- Journal Volume: 124; Journal Issue: 1; Journal ID: ISSN 1520-6106
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-ray absorption near edge spectroscopy; X-rays; Light absorption; Absorption; Oscillation
Citation Formats
Miller, Nicholas A., Michocki, Lindsay B., Konar, Arkaprabha, Alonso-Mori, Roberto, Deb, Aniruddha, Glownia, James M., Sofferman, Danielle L., Song, Sanghoon, Kozlowski, Pawel M., Kubarych, Kevin J., Penner-Hahn, James E., and Sension, Roseanne J. Ultrafast XANES Monitors Femtosecond Sequential Structural Evolution in Photoexcited Coenzyme B12. United States: N. p., 2019.
Web. doi:10.1021/acs.jpcb.9b09286.
Miller, Nicholas A., Michocki, Lindsay B., Konar, Arkaprabha, Alonso-Mori, Roberto, Deb, Aniruddha, Glownia, James M., Sofferman, Danielle L., Song, Sanghoon, Kozlowski, Pawel M., Kubarych, Kevin J., Penner-Hahn, James E., & Sension, Roseanne J. Ultrafast XANES Monitors Femtosecond Sequential Structural Evolution in Photoexcited Coenzyme B12. United States. https://doi.org/10.1021/acs.jpcb.9b09286
Miller, Nicholas A., Michocki, Lindsay B., Konar, Arkaprabha, Alonso-Mori, Roberto, Deb, Aniruddha, Glownia, James M., Sofferman, Danielle L., Song, Sanghoon, Kozlowski, Pawel M., Kubarych, Kevin J., Penner-Hahn, James E., and Sension, Roseanne J. Wed .
"Ultrafast XANES Monitors Femtosecond Sequential Structural Evolution in Photoexcited Coenzyme B12". United States. https://doi.org/10.1021/acs.jpcb.9b09286. https://www.osti.gov/servlets/purl/1605287.
@article{osti_1605287,
title = {Ultrafast XANES Monitors Femtosecond Sequential Structural Evolution in Photoexcited Coenzyme B12},
author = {Miller, Nicholas A. and Michocki, Lindsay B. and Konar, Arkaprabha and Alonso-Mori, Roberto and Deb, Aniruddha and Glownia, James M. and Sofferman, Danielle L. and Song, Sanghoon and Kozlowski, Pawel M. and Kubarych, Kevin J. and Penner-Hahn, James E. and Sension, Roseanne J.},
abstractNote = {Polarized X-ray absorption near-edge structure (XANES) at the Co K-edge and broadband UV-vis transient absorption are used to monitor the sequential evolution of the excited-state structure of coenzyme B12 (adenosylcobalamin) over the first picosecond following excitation. The initial state is characterized by sub-100 fs sequential changes around the central cobalt. These are polarized first in the y-direction orthogonal to the transition dipole and 50 fs later in the x-direction along the transition dipole. Expansion of the axial bonds follows on a ca. 200 fs time scale as the molecule moves out of the Franck-Condon active region of the potential energy surface. On the same 200 fs time scale there are electronic changes that result in the loss of stimulated emission and the appearance of a strong absorption at 340 nm. These measurements provide a cobalt-centered movie of the excited molecule as it evolves to the local excited-state minimum.},
doi = {10.1021/acs.jpcb.9b09286},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 1,
volume = 124,
place = {United States},
year = {2019},
month = {12}
}
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